Treating hydrocarbons



Sept. 29, 1931. E. R. WOLCOTT 1,825,294

TREATING HYDROCARBONS Filed June 14, 1924 351 Gwen 1401;;

umrso is'ra'rss PATENT; oFFica IDSOH nawowo'ra', 01 PORT THUR, TRA S,ASSIGNOB, BY IESNE ASSIGNMENTS, 1'0

TH] arms COIPAHY, 0! NEW YORK, I. Y. A CORPORATION 01' DEL AWL rmrmcmnocmons Application m June 14. 1924. Serial 1 .71am.

This invention relates to the treatment of hydrocarbons with certainmaterials to effeet a conversion of higher boiling hydrocarbons intolower boiling hydrocarbons, and relates particularly to improvements inmethods of treatment in which metallic halids,

' such as aluminum chlorid, are employed.

I have found that if the hydrocarbons be .heated or distilled in thepresence of a me- 10 tallic halid, such as aluminum chlorid, and if theheating or distillation be carried on in the presence of hydrogenchlorid, or while introducing the hydrogen chlorid into the still thatan efiectual conversion of higher s boiling point products into lowerboiling products may be obtained. The addition of the h drogen chlorid--insures an even and smoot operation of the still and materiallyincreases the yield of lower boiling products.

so The invention is such that it can be most conveniently described byreference to certain apparatus adapted for carrying out the process. Theaccompanying drawing is '8. diagrammatic elevation of an apparatussuitable or this purpose.

In the a paratus thus illustrated a stil1 10.

is arrange to be heated by any suitable heatingmeans (not shown) andprovided with a charging line 11 for introducing the hydrocarbonmaterial to be treated, a charging conduit 12 for admitting the treatingmaterial, and a draw-ofi pipe 13 for drawing oil .residue. The still isequipped with a vapor line 14 which may extend to one or more aircondensers 15, or other suitable refluxing or fractionating means, fromwhich a vapor line 16 extends to a outlet 18.

For introducing the hydrogen chlorid a pipe 19 is provided whichpreferably depends into the still to a point near the bottom thereof.The pipe 19 may terminate in one or more spray pipes, as the perforatedpipe 20, in order to thoroughly 'difiuse the hydrogen chlorid throughthe mass in the still. If desired, a layer of porous or permeable mate:rial may be placed in the still and the hydrogen chlorid caused to beintroduced by dif-' fusion through the porous substance therebyapparatus which has hitherto been considere condenser 17 provided withan.

admitting the gas in a finely divided state and thoroughly comminglingit with the materials in the still. a Y r In the operation of theprocess the hydrocarbon material to be treated, which may be a petroleumproduct such as gas oil, or kerosene, or other hydrocarbon oil whichit'is desired to convert into a lower boiling oil, is in-.

- troduced through the pipe 11. A suitable metallic halid, preferablyanhydrous aluminum, chlorid, is charged through the pi 12, either in theform of the lum or ulveru ent chlorid or in the form of a l1qui obtainedby ing the chlorid with a suitable solvent or car-- rier, such ashydrocarbon oil or other suitable protective medium in which. the.chlorid is dissolved or contained. The hydrochloric acid gas-isintroduced through the pipe 19 and thence through the spray pipe 20, or4 through porous material or other sultable diffusing means, into themass in the still. The lower boiling point product obtained mayberemoved as a condensate through the condensate outlet 18.

' The use of mixing, stirring, or scrapin 75 necessary in carrying onthe treatment of oils with aluminum chlorid is practically. dispensedwith in the practice of my invention, since the passage of the hydrogenchlorid gas through the mass in the still produces an effectiveagitation tending to prevent the sludge and tarry matters fromcollecting and coking in the bottom of the still and bringing about goodcontact between the catalyst and the hydrocarbon material. Stirring,agitating or scraping mechanism may, however, be employed, if desired.

An idea whlch induced the present invention was that by passing thehydrogen chlorid through the hydrocarbon material in the presence ofaluminum chlorid (AhCh) it might be possible to cause a hydrogenatingefiect'by combining the hydrogen with the heavier hydrocarbons toincrease the yield of lighter and more saturated hydrocarbons, while atthe same'time the chlorin would operate to regenerate the aluminumchlorid.

It may be, however, that the reaction is not a hydrogenating one; infact, I do not undertake to explain the chemical reactions which 100occur in the practice of my invention. It is sufiicient to state that inconductingthe treatment of hydrocarbons with a treatm mate'- rial, suchas aluminum chlorid, the e ectiveness of the operation is increased bythe addition of extraneous hydro n chlorid.

meme

when the reaction has proceeded to the desiredextent.

In witnem whereof I have hereunto set my handthis22n in one method ofcon ucting my process the hydrocarbon material is first saturated withhydrogen chlorid, after which the aluminum chlorid is added and thedistillation carried on. In the preferred method of opera-- tion,however, the hydrogen chlorid gas is introduced into the still duringthe distillation.

The hydrogen chlorid em loyed in the practice of the invention may e inthe form of dry as or moist hydro en chlorid or hydroch oric acid may beeinp oyed, since the presence of moisture or the a ueous solution causesthe production of hydrogen chlorid due to the decomposition of thealuminum chlorid by water. if desired, water itself may be added to thetreating vessel or moist oil may be admitted thereto, the presence ofthe moisture insuring the production of the necessary hydrogen chlorid.

()bviousiy, various modifications oi the invention may effected withoutdeparting from the spirit ens scope ofthe invention.

\ u u d I The true scope of the invention is defined 1n the appendedclaims.

What 1 claim is: 1. The process of treatinr hydrocarbon oils to sheetconversion'of higher boiling hydrocarbons into lower boilinghydrocarbons which comprises chewing a high boiling petroleum oil, and acatai anhydrous aluminum chloride to a still, maintaining said still ata temperature suficient to sheet material conversion of the oil therein,introducing hydrogen chloride into.

said still to thoroughly commin is with the oil and aluminum chloride,where y a smooth evolution of vapors is obtained and the aluminumchloride is maintained in an active condition, condensing the evolvedvapors to form a distillate of low boilig hydrocarbons, and withdrawing,before substantial accumulation of coke ocurs, the residual liquid fromthe still-for disposal without further treatment.

2. The process of treating hydrocarbon oils to sheet conversion ofhigher boiling hydrocarbons into lower boiling hydrocarbons whichcomprises subjecting a higher boiling petroleum oil to distillation temratures in the presence of a catalyst consist1n solely of anhydrousaluminum chloride, intimately commingling hydrogen chloride with the hotmixture of oil and aluminum chloride to produce an even evolution ofvapors of low boilin hydrocarbons and to prevent the oil and a uminumchloride from coking, subjecting the evolved vapors to dephlegmation toproduce a vapor fraction of the desired quality and wit drawing theunvaporized residue, which is not returned to the still,

yet consisting solely of d da of Ma 1924.

i E SON WQLCOTT.

